Materials for storage and release of bulk quantities of hydrogen and methods of making and using same

ABSTRACT

The invention relates to materials for storing and releasing bulk quantities of hydrogen and methods for preparing and using same. The materials exhibit fast release rates at low release temperatures are suitable as hydrogen sources for a variety of applications and devices.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority from and is a divisional of U.S. patentapplication Ser. No. 10/778,997 filed by the same inventors on Feb. 12,2004 and entitled MATERIALS FOR HYDROGEN STORAGE AND METHODS FORPREPARING AND USING SAME, the contents of which are hereby incorporatedby reference.

This invention was made with Government support under ContractDE-AC0676RLO-1830 awarded by the U.S. Department of Energy. TheGovernment has certain rights in the invention.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

The present invention generally relates to materials and processes forstoring hydrogen, and uses thereof. More particularly, the presentinvention relates to compounds, materials, and material combinationshaving a greater capacity for both storing hydrogen and for releasinghydrogen at lower release temperatures and faster release rates, forapplications both on-board and off-board.

(2) Description of Related Art

The Department of Energy (DOE) issued a challenge for hydrogen storagerelated technologies during 2003 to compliment existing programs onHydrogen Production and Fuel Cell development. Part of the challengeinvolved proposed project milestones in calendar years 2010 and 2015 forthe development of new materials and technologies relating to storinghydrogen for use as vehicle energy sources. Four technologies forstoring hydrogen are under investigation in the technical art: (1)storage as simple metal hydrides, e.g., MgH₂, (2) storage on carbonmaterials, including single-walled carbon nanotubes, (3) storage ascomplex metal hydrides, e.g., NaAlH₄, and (4) chemical hydrogen storage,e.g. NH_(x)BH_(x), where x=1 to 4. The technical developments related tochemical hydrogen storage technology are discussed further hereafter.

Baitalow et al. (Thermochimica Acta 391, 2002, 159-168) have shown thepotential for use of N—B—H compounds including ammonia borane, NH₃BH₃,(AB) as a hydrogen storage material. Jaska et al. (J. Am. Chem. Soc.2003, 125, 9424-9434) report hydrogen formation in AB is likely to occurby an intermolecular dimerization pathway as shown in reaction (1),although a two-step mechanism, as shown in reactions (2) and (3), is notruled out:

2NH₃BH₃→NH₃BH₂—NH₂BH₃+H₂  (1)

NH₃BH₃→NH₂═BH₂+2H₂  (2)

2NH₂═BH₂→NH₃BH₂—NH₂BH₃  (3)

Each step that forms a new B—N bond also forms hydrogen, as illustratedin reactions (4) and (5):

NH₃BH₃+NH₃BH₂—NH₂BH₃→NH₃BH₂—NH₂BH₂—NH₂BH₃+H₂  (4)

NH₃BH₃+NH₃BH₂NH₂BH₂—NH₂BH₃→NH₃BH₂—(NH₂BH₂)₂—NH₂BH₃+H₂  (5)

Baitalow et al. further report that at temperatures >150° C., additionalhydrogen may be released, as illustrated in reactions (6) and (7):

(NH₃BH₂NH₂BH₂—NH₂BH₃)_(n)→(NH₃BH₂NH₂BH═NHBH₃)_(n)+H₂  (6)

(NH₃BH₂NH₂BH═NHBH₃)_(n)→(NH₃BH═NHBH═NHBH₃)_(n)+H₂  (7)

However, it is well known in the art that release of hydrogen from bulkor neat AB occurs at temperatures at which undesirable side reactionsoccur thereby generating products that contaminate and decrease thepurity of the released hydrogen available as fuel. For example, theformation of cyclic borazine, c-(NHBH)₃, an inorganic analog of benzene,is one such contaminating product reported by Wideman et al. (Inorg.Chem. 1995, 34, 1002-1003), illustrated in reaction (8):

(NH₃BH═NHBH═NHBH₃)_(n) →n(NHBH)₃+H₂  (8)

Raissi et al. (“Hydrogen Storage in Ammonia and Aminoborane Complexes”,Hydrogen Program Annual Review, May 21, 2002) have reviewed data forhydrogen release from the neat or bulk solid AB. The reaction of NH₃BH₃to yield NH₃(BH₂—NH₂)_(n)BH₃+free nH₂, releases hydrogen at temperaturesnear 115° C. in reactions that are comparatively slow and that againhave a high potential for forming borazine. At even moderate reactiontemperatures, e.g., >150° C., borazine yields are significant. Borazineis damaging to fuel cells. Thus, its presence means the purity ofreleased hydrogen remains questionable and thus unsuitable for use.

As the current state of the art shows, use of AB materials remainsproblematic due to 1) relatively high reaction temperatures required forhydrogen release, 2) slow rates for release, and 3) presence of reactionproducts like borazine that contaminate the hydrogen released from thesource materials complicating their use as a fuel source.

Accordingly, there remains a need to 1) decrease the temperatures underwhich hydrogen is released so as to meet proposed guidelines for fuelstorage and use, 2) improve the rates for hydrogen release, and/or 3)minimize unwanted side reactions that generate undesirable andcontaminating products thereby increasing the purity of hydrogenavailable as fuel.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide materials, materialcombinations, and/or compositions for storing and releasing hydrogenthat decrease the temperatures and improve the rates for hydrogenrelease thus meeting the objectives for provision of hydrogen sourcesfor next-generation fuel source applications. It is still further anobject of the present invention to control reactivity so as to minimizeundesirable reaction products that contaminate the released hydrogenfrom hydrogen storage materials, thereby increasing the purity ofreleased hydrogen available as fuel. Materials of the present inventionprovide greater capacities for storage and release of hydrogen in a purestate, at both lower temperatures and faster rates, and thus have thepotential to serve numerous industrial applications wherein highhydrogen storage and usage demands may be met, including, but notlimited to, next generation fuel cells and hydrogen sources, applicableto uses in the automobile industry and elsewhere.

The material of the present invention for storing and releasing hydrogencomprises 1) a support comprising a high surface area material that is2) combined with at least one compound capable of storing and releasinghydrogen such that when combined with the support is capable ofreleasing hydrogen at a greater rate and a lower temperature relative tothe bulk or neat compound(s).

The term “high surface area” as used herein means a surface area of atleast 50 m²/g. The term “support” means a high surface area materialformulated, structured, formed, or configured to support a bulk hydrogenstorage material. The support materials of the present invention, forexample, serve as substrates whereby a bulk quantity of a hydrogenstorage and release material is deposited, impregnated, coated, and/orpolymerized thereon at correct weight ratios.

The material for storing and releasing hydrogen currently and preferablycomprises a member selected from the group of N—B—H compounds,including, but not limited to, ammonia borane (AB) that when depositedonto a support or scaffolding material, the composition exhibits uniqueand useful properties for storing and releasing hydrogen. Othermaterials suitable for hydrogen storing and releasing compounds ormaterials comprise the group of chemical hydrides, complex hydrides,metal hydrides, polymers, conducting polymers, and nitrogen boroncompounds, boron nitride, carbon materials, and combinations thereof.

Support materials include, but are not limited to, members selected fromthe group of porous materials, interconnected materials,non-interconnected materials, channeled materials, aerogels, aerogelmaterials, polymer materials, porous polymer materials, nonporousmaterials, mesoporous materials, zeolites, zeolite materials, silica,silicon dioxide, mesoporous silica, titanium dioxide, mesoporoustitanium dioxide, carbon materials, mesoporous carbon materials, andcombinations thereof.

The method of preparing the hydrogen storage materials of the instantinvention comprises the steps: 1) providing a support composed of a highsurface area material, and 2) combining the support with at least onecompound capable of storing and releasing hydrogen, wherein thecompound(s) when deposited on the support releases hydrogen at a greaterrate and a lower temperature relative to the bulk or neat material. Theterm “combining” as used herein describes various chemical and physicalprocesses, including, but not limited to impregnating, depositing,layering, coating, physisorbing, chemisorbing, mixing, wetting,polymerizing, chemically bonding, and combinations thereof. Theresulting composite material for storing and releasing hydrogen may beadapted for both on-board and off-board applications, including but notlimited to, on-board devices, off-board devices, hydrogen generators,fuel sources and components, components in solid oxide fuel cells, aswell as constituents and/or components in/for engines, including, butnot limited to, vehicle engines, combustion engines, automobile engines,and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the invention will be readily obtainedby reference to the following description of the accompanying drawingsin which like numerals in different figures represent the samestructures or elements.

FIG. 1 a shows a high resolution transmission electron microscope(HRTEM) cross-sectional view of a porous templated silicate structure,SBA-15, used in conjunction with an embodiment of the present invention.

FIG. 1 b shows a HRTEM transverse view of the SBA-15 porous templatedsilicate structure of FIG. 1 a.

FIG. 2 shows the unique temperature profile for release of hydrogen froma 1:1 AB:SBA-15 composite compared to neat AB, according to anembodiment of the invention.

FIG. 3 presents mass-spectral data for release of hydrogen as a functionof DSC thermal decomposition temperature for a 1:1 AB:SBA-15 composite,a 2:1 AB:SBA-15 composite, and a 3:1 AB:SBA-15 composite according todifferent embodiments of the invention.

FIG. 4 presents mass-spectral data for release of hydrogen as a functionof DSC thermal decomposition temperature for a 1:1 AB:SBA-15 compositeshowing a significantly lower hydrogen release temperature with anabsence of contaminating reaction products.

FIG. 5 compares rate data (log 1/τ_(1/2) vs 1/T) for release of hydrogenfrom a 1:1 AB:SBA-15 composite compared to neat AB, according to anembodiment of the invention.

FIG. 6 presents mass-spectral data for release of hydrogen as a functionof DSC thermal decomposition temperature for a 1.77:1 AB:MCM-41composite, according to another embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

While the present invention is described herein with reference to thepreferred embodiments thereof, it should be understood that theinvention is not limited thereto, and various alternatives in form anddetail may be made therein without departing from the spirit and scopeof the invention. In particular, those skilled in the art willappreciate that materials described herein for hydrogen storage/release,as well as related moieties, like chemical products and/or intermediatescan be applied to numerous template or support substrates, both of aporous or nonporous nature. The term “pores” as the term is used indescribing porous materials include, but are not limited to,interconnected, non-interconnected, ordered, non-ordered, channels,configurations, features, designs, and combinations thereof. Forexample, a macroscale support material comprising a plurality ofnanoscale features, nanoscale channels, or nanoscale pores. The term“pore” further embodies and encompasses all shapes, including, but notlimited to, round and square. Other embodiments for pore, channel, andfeature configurations as would be envisioned by a person of ordinaryskill in the art are hereby incorporated, as well as the associatedmaterial manufacturing and/or application methods. Thus, no limitationin intended by the disclosure of the preferred embodiments.

The support of the present invention is preferably selected from thegroup consisting of high surface area materials, including both porousand non-porous materials, and combinations thereof. FIG. 1 a and FIG. 1b show high resolution transmission electron microscope (HRTEM) imagesof a support 100 comprising a macroscale silica template material,SBA-15 (SBA), in cross-section and transverse views, respectively. Theterm “template” as used herein describes support materials on which thehydrogen storage and release materials of the present invention areimpregnated, deposited, coated, chemisorbed, physisorbed, and/orchemically bound in a fashion corresponding to the nature of thesurfaces (both interior and exterior) of the substrate therebycontouring, mimicking, and/or mirroring the detail or pore structure ofthe substrate surface on which it is deposited or in chemicalcommunication with. Porous silica templates have an extremely highsurface area and a highly ordered pore structure, as reported by Zhao etal. (Science, Vol. 279, 23 Jan. 1998). Silica (SiO₂) is a preferredsupport for the template reactions of the present invention by virtue ofthe pore structure. The support comprises a plurality of pores orchannels. The pores of the support materials of the present inventionare preferably in the range from about 2 angstroms (Å) to about 1000micrometers (μm). More preferably, pores of the support materials of thepresent invention range from about 2 nanometers (nm) to about 100 μm.Suitable alternative materials for the support include porous carbonand/or porous titanium dioxide (TiO₂), including, e.g., mesoporouscarbon and/or mesoporous titanium dioxide. “Mesoporous” as used hereinmeans pores of a size in the range from about 2 nm to about 0.05 μm. Thesupport may be further formulated in a variety of shapes or particleconfigurations specific to the intended application. For example, thesupport materials may be comprised of, e.g., nanoparticles, nanospheres,colloidal particles, and combinations or variants thereof. Particles inthese embodiments are preferably of a size in the range from about 1 nmto about 10 μm.

The support 100 is combined with at least one compound having a highweight or volume ratio density of hydrogen, although more than onecompound can be envisioned. Materials for storing and releasing hydrogenpreferably comprise at least one element selected from the groupconsisting of Li, Be, B, C, N, O, Na, Mg, Al, Si, P, S, and combinationsthereof. More preferably, materials for storing and releasing hydrogenare selected from the group of NH_(x)BH_(x) compounds where x is in therange from about 1 to 4, ammonia borane (NH₃BH₃) being representative,but not exclusive. For example, metal hydrides, complex hydrides, otherchemical hydrogen storage materials (e.g., ammonia, NH₃), and/ormixtures thereof can be envisioned. Combining the support and thecompound(s) having a high weight percentage of hydrogen produces amaterial exhibiting the uncharacteristic properties of a faster releaserate and a lower release temperature for hydrogen relative to the bulkor neat materials themselves.

Ammonia borane (AB) as a hydrogen storing and releasing material in theinstant case is preferably deposited or fashioned at thicknesses wherebythe AB hydrogen storage and releasing material is combined at a 1:1weight ratio with the support 100 or scaffolding substrate therebyyielding a 1:1 composite material, e.g., 1:1 AB:SBA-15, but is notlimited thereto. For example, other weight ratios between the ABhydrogen storing and releasing material and the SBA support are easilyaccommodated. For example, AB:SBA weight ratios of 1:2, 1:3, andgreater, or alternatively AB:SBA weight ratios of 2:1, 3:1 and greatermay be deployed to maximize hydrogen storage and release. Choices forconsideration as would be envisioned by a person of ordinary skill inthe art are hereby incorporated.

Porous materials used as the support 100 or template material preferablycomprise at least about 20% porosity by volume. The high surface areasupport material is preferably selected from the group consisting ofporous nanoparticles, porous coated nanoparticles, and combinationsthereof. Porous coated nanoparticles may be selected from the groupconsisting of externally coated, internally coated, bothexternally/internally coated, internally filled, internallyfilled/externally coated, and combinations thereof.

Non-porous materials may be used as supports or scaffold materials andare preferably selected from the group of non-porous nanoparticles,externally coated non-porous nanoparticles, and combinations thereof.Examples of a non-porous support include, but are not limited to, acomposite comprising nanoscale features or channels, e.g., non-porousnanoparticles and/or non-porous nanospheres.

It should be noted that to further enhance the kinetics orthermodynamics for hydrogen release and uptake, catalysts and catalystlike materials may be added to the support(s), hydrogen storagematerial(s), or the combined support/hydrogen storage composites. Forexample, adding a transition metal catalyst and/or a carbon material tothe composite. Catalysts as would be envisioned or deployed by a personof ordinary skill in the art are hereby incorporated.

Solvent choices for preparing the materials of the present invention aremyriad, including liquids or supercritical fluids of water, ammonia, andcarbon dioxide. Other solvent selections include hydrocarbon and organicsolvents such as methanol, ethanol, and diethyl-ether. Methanol is apreferred solvent for dissolution and deposition of the hydrogen storingand releasing material due to its rapid drying whereby the AB materialis quickly and efficiently combined, deposited and/or bonded to thesupport. Other similarly volatile and/or fast drying solvents may beselected. Thus, no limitation in the selection of applicable solvents ishereby intended by the disclosure of the preferred solvent.

The following examples are intended to promote a further understandingof the present invention. Example 1 details the preparation of a 1:1AB:SBA-15 composite material, according to an embodiment of the presentinvention, and compares hydrogen release temperatures relative to theneat or bulk AB material. Examples 1-4 describe and compare othersproperties of the AB:SBA-15 composite material and another compositematerial of the present invention relative to the neat or bulk ABmaterial.

EXAMPLE 1

Hydrogen release temperatures were compared for a 1:1 AB:SBA-15composite against release temperatures for the neat and/or bulk ABmaterial.

Experimental. A support 100, SBA-15, comprising mesoporous silica with aplurality of hexagonally ordered nanoscale pore channels was prepared asdescribed, e.g., by Zhao et al. (Science, Vol. 279, 23 Jan. 1998),incorporated in its entirety herein. In a typical preparation of SBA-15,12.0 g of non-ionic surfactant comprising ethylene oxide/propylene oxideblock copolymer (M.W. approx. 5,800) sold commercially under thetradename PLURONIC® P-123 non-ionic surfactant (BASF Corp., Mount Olive,N.J.) was dissolved in 360 mL of 2M HCI solution at 40° C. 25.5 g of 98%tetra-ethyl-ortho-silicate (TEOS), available commercially (Sigma-AldrichCorp., St. Louis, Mo.), was added to the milky solution and stirred for18 hours at the same temperature. The mixture was transferred into ateflon-lined autoclave and heated to 100° C. for 24 hours withoutstirring. The white precipitate was filtered, dried in air, and calcinedat 550° C. for 6 hours. Thin sections of the resultant support specimenwere subjected to high resolution transmission electron microscopy(HRTEM) observation, prepared by standard epoxy embedding followed byultra-microtoming, e.g., slicing, to a thickness of 50 nm or less. Thesupport material 100 was found to have an average particle size of from100-200 μm, an average surface area of approximately 1000 m²/g, and apore and/or channel diameter starting at about 3 nm.

The hydrogen storage and release material, ammonia borane (AB), wasprepared for use in combination with the support 100 as follows. 90%technical grade AB (Sigma-Aldrich Corp., St. Louis, Mo.) was purified byrecrystallization from diethyl ether, followed by washing with ethanolto remove polymeric and borate impurities, thereby yielding >99% pureNH₃BH₃, as shown by ¹¹B Nuclear Magnetic Resonance (NMR) imaging.

Deposition and/or coating of the purified AB to the support 100 weredone as follows. 50 mg of purified AB was dissolved in 0.3 mL methanolafter which a 50 mg sample of the SBA-15 support material was wettedwith the methanol solution. Given the porous nature of the support,capillary action rapidly filled the internal channels and pores of themesoporous template material. The ‘wet’ SBA-15 was dried under vacuum toremove the methanol solvent, yielding a AB:SBA composite material havinga 1:1 weight ratio of AB to SBA-15 in the composite. Clumping of thesolid AB on the template can be expected if the internal channels arenot successfully coated. However, SEM images (not shown) of the SBA-15material before and after coating with AB showed very similar features,and an absence of clumping.

HRTEM analyses were carried out on a Jeol JEM Model 2010 microscope(JEOL USA, Inc., 11 Dearborn Rd., Peabody, Mass., 01960) having aspecified point-to-point resolution of 0.194 nm. The operating voltageon the microscope was 200 keV. All images were digitally recorded (imagesize 1024×1024 pixels) with a Gatan slow scan model 692-0100 camerasystem (Gatan, 5933 Coronado Lane, Pleasanton, Calif.). Image processingwas carried out using Digital Micrograph™ version 3.1 software (GatanInc., Pleasanton, Calif.). Differential Scanning Calorimetry (DSC)analyses of the neat AB material and the chemically combined AB:SBA-15material were performed using a Netzsch STA 409 combination ThermalGravimetric Analyzer (TGA) and Differential Scanning Calorimeter (DSC)(NETZSCH Instruments, Inc. 37 North Ave. Burlington, Mass. 01803) oralternatively a Setaram C80 Calorimeter (Setaram, 7 rue de l'Oratoire69300 Caluire, FR) in combination with a Pfeiffer QMS300 MassSpectrometer (Pfeiffer Vacuum Ltd., 2-4 Cromwell Business Centre, HowardWay, Interchange Pk, Newport Pagnell, Bucks MK16 9QS, UK) equipped witha standard electron impact ionization detector. In the Netzschequipment, a heated fused silica capillary (200° C.) was used totransfer the off gas from the TGA to the mass spectrometer (MS). Athermal temperature ramp of 1° C./min over a temperature range from roomtemperature to about 250° C. at an argon flow of 40-100 cc/min was used.The MS scanning rate was 12 seconds for a range of 1 to 100 amu.

Results. FIG. 2 compares hydrogen release curves determined by massspectrometric analysis for neat AB 210 and 1:1 AB:SBA-15 composite 220as a function of DSC thermal decomposition temperature. DSC results showhydrogen was released from the 1:1 AB:SBA-15 composite in thetemperature range from about 25° C. to about 200° C. with a peakexotherm 230 for hydrogen release occurring at 79.4° C., well below the100° C. objective. The neat AB 210 in comparison released hydrogen inthe temperature range from 74° C. to 200° C. with the peak releaseexotherm 240 occurring at about 97.6° C. As shown in FIG. 2, releasetemperature in the 1:1 composite 220 is reduced by a factor of about 23percent compared to the neat material 210. If reaction (1) is thecorrect mechanistic pathway, then it follows that the dimerizationreaction forms oligomers through subsequent bimolecularde-hydro-polymerization pathways. The result observed for the 1:1composite is especially attractive given that a fundamental requirementfor on-board vehicle storage is the release of hydrogen at temperaturessignificantly below 100° C., an objective met by the 1:1 AB:SBAcomposite in Example 1.

EXAMPLE 2

Composites of AB:SBA-15 at weight ratios greater than 1:1 were used tocompare hydrogen yields with the neat AB material. Expectation was thatthe hydrogen release temperatures from these composites would be reducedcompared to the neat material.

Experimental. Composite materials were prepared as in Example 1 atweight ratios for AB to SBA-15 of 2:1 and 3:1 and compared to resultsfor both the 1:1 composite and the neat AB material.

Results. FIG. 3 presents results comparing mass-spectral (MS) data forhydrogen release as a function of DSC thermal decomposition temperaturefor a 2:1 AB:SBA-15 composite 320 material and a 3:1 AB:SBA-15 composite330 material relative to the 1:1 AB:SBA-15 composite 340 and neat AB310. In the figure, maximum exotherm temperatures for hydrogen releasein the 2:1 composite 320 and the 3:1 composite 330 were 89.9° C. and92.7° C., respectively. These compare with a release temperature for the1:1 composite 340 of 79.4° C. and for neat AB 310 of 97.6° C.,respectively. Results show that while the hydrogen release temperaturesfor the greater weight ratio composites are above those for the 1:1composite 340, release temperatures for the 2:1 composite and 3:1composite are still operable below the 100° C. benchmark, exhibitingtemperature reductions for release of hydrogen of about 8% and about 5%,respectively, compared to neat AB 310.

EXAMPLE 3

In order to achieve peak fuel performance, the cyclization reaction thatforms borazine (FW=80.47), illustrated in reaction (8), must beminimized and the desired dehydrogenation reactions shown in reactions(6) and (7) optimized. Samples of the 1:1 AB:SBA-15 test material wereused to test the hypothesis that the yield of borazine would be reducedin the 1:1 AB:SBA-15 test material when heated, compared to the neat orbulk AB material. If, as expected, the AB was coated on the inside ofthe mesoporous silica (e.g., SBA-15) template 100, the expectation wasthat the template would minimize borazine formation by controllinglinear polymer growth and minimizing the undesired cyclization reaction.

Experimental. Differential scanning calorimetry (DSC) experiments wereconducted with concurrent collection of mass-spectral (MS) data tocompare samples of neat AB material to test samples of 1:1 AB:SBA-15material prepared as in Example 1. DSC scan temperature was from 20-200°C. at a scan rate of 5° C./min under an argon purge of 40 cc/min. Massdata were collected at mass numbers 2, 79, 80, and 81, corresponding tohydrogen, borazine, and two daughters of borazine, respectively.

Results. FIG. 4 presents results comparing mass-spectral (MS) data as afunction of DSC thermal decomposition temperature for the 1:1 AB:SBA-15material and the neat AB. In the figure, MS data curves are showncorresponding to mass numbers 2, 79, 80, 81 for hydrogen 410, borazine420, and two borazine daughter products, curves 430 (m−1 daughter) and440 (m+1 daughter), respectively.

Thermolysis of the AB material in the SBA-15 template (e.g., as 1:1AB:SBA-15) shows two profound effects different than observed in thebulk thermal reaction. First, hydrogen is released from the AB in thesupport or template material at lower temperatures, e.g., below 100° C.Secondly, borazine is not detected or observed in the AB thermolysisfrom the mesoporous template SBA-15, in direct contrast withobservations for the neat AB material that show borazine is formedduring thermolysis of the bulk (e.g., unbound) and/or neat AB. Even atthe reduced argon flow rates of 40 cc/minute, no borazine was detected,or was substantially below the detection limit of the mass detector.Further, hydrogen continues to be released from the compositeeffectively without the interference or presence of contaminatingreaction products up to about 170° C., a temperature that routinelycorresponds with borazine formation during heating of the neat AB.Results demonstrate that use of the AB:SBA-15 composite, including testcases with mesoporous silica templates 100 (e.g., SBA-15), can be usedto control the reactivity of the dehydropolymerization chemistry ofammonia-borane (AB) to yield gaseous hydrogen.

Further, that the reactivity of the gaseous reactants in the presentcomposite can be controlled has far-reaching implications. For example,it has been demonstrated that undesirable and/or contaminating gases canbe contained or confined within the porous structure and that thedesired gases can be released favorably and in a pure state. This meansthere is selective control of gaseous diffusion and release using themesoporous substrates whereby various reactant gases can be successfullyexploited to enhance control and reaction and release of desired gasesor other end products relative to the undesirable ones. One may be ableto show similar control of reactant gases, e.g., NH₃, reacted and/orreleased from other comparable composites or storage materials.

EXAMPLE 4

Rates for hydrogen release as a function of thermal decompositiontemperature for the 1:1 AB:SBA-15 test material (prepared as detailed inExample 1) were compared to release rates for neat AB.

Experimental. DSC experiments were conducted on test samples of the 1:1AB:SBA-15 composite material and neat AB material at several differentisothermal temperatures, in the range from about 40° C. to about 60° C.The peak of the DSC curve corresponding to the peak of the hydrogenrelease from the first reaction step, e.g., AB-→polymer+H₂ for the bulkAB material and the Support material can be compared at othertemperatures from the slope of the lines taken from plots of log1/τ_(1/2) (where τ_(1/2) is the half-life for hydrogen release in unitsof time) vs. 1/T (where T is the temperature) for the AB:SBA-15 comparedto neat or bulk AB.

Results. FIG. 5 compares instantaneous rate data for the thermaldecomposition of AB in the 1:1 AB:SBA-15 composite 510 and for neat AB520, as a function of hydrogen release temperature. The rate differencefor hydrogen release between curves 510 and 520, as measured by thevertical displacement, is approximately two log units in the instantcase, indicating the rate of hydrogen release from the 1:1 AB:SBA-15composite 510 material compared to the neat AB 520 is up to 2 orders ofmagnitude greater than from the neat AB, or about 100 times faster. Evenat 1 order of magnitude, a rate 10 times faster than the neat ABmaterial would be expected. Further, the temperature differences notedfor the 2:1 and 3:1 weight ratio composites mean these compositesexhibit release rates greater than the neat or bulk material as well.Other configurations and/or ratios for the composite material(s) may beequally useful, e.g., 1:2 SBA, for example.

The person of ordinary skill will recognize that similar results may beexpected using other composite support materials and/or materialcombinations. For example, composites comprising metal hydrides, orcomplex metal hydrides, as well as AB combined with other substrates.Thus, no limitations are intended by the disclosure of rate data for the1:1 AB:SBA-15 composite.

EXAMPLE 5

In another embodiment of the present invention, a 1:1 weight ratiocomposite was prepared between AB and silica (SiO₂)nanospheres/nanoparticles, e.g., AB:SiO₂, prepared as detailed inExample 1.

Experimental. DSC experiments were conducted and hydrogen releasetemperatures were measured by mass spectrometric analysis for theAB:SiO₂ composite. Results were then compared to data collected for 1:1AB:SBA-15 and for neat AB.

Results. Hydrogen release exotherms for the 1:1 AB:SiO₂ composite werecomparable to those observed for 1:1 AB:SBA-15, with a slightly highertemperature for release of hydrogen relative to the AB:SBA-15 material.

In general, the reduction in temperatures for hydrogen release in thehydrogen storing and releasing materials deposited on supports orscaffolds (e.g., SBA-15 and SiO₂ nanospheres, for example) appears to bea catalytic effect but may also be linked to differences in thecurvature radii for the nanoscale templating materials. The variousmaterial combinations/composites with AB clearly show unexpected andnotable differences in hydrogen release profiles relative to the neat ABalone.

EXAMPLE 6

In another embodiment of the present invention, a 2:1 (e.g., 1.77:1)weight ratio composite between AB and another mesoporous silicatematerial, sold under the tradename MCM-41™ (Mobile Oil Corp., Fairfax,Va.), was similarly prepared for use as detailed in Example 1. MCM-41comprises arrays of non-intersecting hexagonal pore channels. Walls ofthe channels are amorphous SiO₂. The width of the channels can becontrolled to be within about 2 to 10 nm. The exceptional porosity up toabout 80% makes MCM-41 a useful support material as with other porousmaterials, including silicas, silica gels, aerogels, and/or zeolites.

Experimental. DSC experiments were conducted and hydrogen releasetemperatures were measured by mass spectrometric analysis for the 1.77:1weight ratio AB:MCM-41 composite. Results were then compared to neat AB.

Results. FIG. 6 shows the hydrogen release exotherm for the 1.77:1AB:MCM-41 composite 610 relative to the neat AB 620. In the figure,temperature for hydrogen release in the AB: MCM-41 composite 610 isabout 81.9° C., which compares with a release temperature from neat AB620 of 97.6° C., a reduction in release temperature of about 16% in theAB:MCM-41 composite 610 relative to the neat material 620. This resultcompares favorably with release temperatures observed for AB:SBA-15composites, and is most closely allied with the results obtained for the2:1 AB:SBA-15 composite 330 in FIG. 3.

In general, the reduction in temperatures for hydrogen release in thehydrogen storing and releasing materials deposited on supports orscaffolds (e.g., SBA-15, SiO₂ nanospheres, and MCM-41) appears to be acatalytic effect but may also be linked to differences in the curvatureradii for the nanoscale templating materials. The various materialcombinations/composites with AB clearly show unexpected and notabledifferences in hydrogen release profiles relative to the neat AB alone.

The properties of the materials of the present invention evidence theirsuitability for uses including, but not limited to, hydrogen storage,fuel generation, and fuel in advance of calendar year 2010 and calendaryear 2015 objectives and milestone established by the Department ofEnergy. For example, materials of the present invention demonstrate ahigh storage capacity for hydrogen in the range up to and includingabout 24% by weight. Greater yields may be likely with various materialcombinations. In addition, results show hydrogen can be supplied at asignificantly faster release rates and lower release and operatingtemperatures by simple heating of the dried solid state materials.Further, materials of the present invention exhibit controlledreactivity whereby the quantity of contaminating reaction products isminimized. Other advantages include low foaming observed during thedegassing process, which factors into the size, configuration, and/orvolume of the containment vessels which ultimately will house theeventual fuels for both on-board and off-board applications. Further,the materials exhibit excellent air and water stability. And, to date,all the reactions involved show a good rationale for reversibility,especially if combined using direct dehydrocoupling. These resultssuggest the present invention materials can be used or tailored for usein next generation fuel sources applicable to combustion engines,including automobile engines in advance of the 2010 and 2015 objectivesfor providing hydrogen fuels.

1. A composition, comprising: a high surface area porous supportcomprising a surface area of greater than or equal to 50 m²/g; and atleast one preselected hydrogen storage compound applied to said highsurface area porous support, said at least one preselected compoundapplied to said high surface area porous support configured toalternatively store or release bulk quantities of hydrogen at a greaterrate and a lower temperature than said at least one preselected compoundwhen not applied to said support.
 2. The composition of claim 1, whereinsaid at least one hydrogen storage compound comprises a member selectedfrom the group consisting of Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P,and combinations thereof.
 3. The composition of claim 2, wherein saidhigh surface area porous support comprises a material selected from thegroup consisting of interconnected porous materials, non-interconnectedporous materials, channeled porous materials, porous silica, mesoporoussilica, porous titanium dioxide, mesoporous titanium dioxide, porouscarbon, mesoporous carbon, porous zeolites, porous aerogels, porouspolymers, and combinations thereof
 4. The composition of claim 1,wherein said at least one hydrogen storage compound is a member selectedfrom the group consisting of hydrides, metal hydrides, conductingpolymers, and nitrogen boron compounds.
 5. The composition of claim 1,further comprising a catalyst.
 6. The composition of claim 5, whereinsaid catalyst is a transition metal catalyst, and said porous supportmaterial is a porous carbon support that includes said transition metalcatalyst.
 7. The composition of claim 1, wherein the hydrogen releaserate from said at least one preselected compound applied to said highsurface area porous support is at least 1 order of magnitude greaterthan said at least one preselected compound not applied to said support.8. The composition of claim 1, wherein said high surface area poroussupport includes said at least one preselected hydrogen storagecompound.
 9. The composition of claim 1, wherein said lower temperaturefor hydrogen release is below about 85° C.
 10. The composition of claim1, wherein said high surface area porous support comprises at least 20%porosity by volume.
 11. A method for making a hydrogen storagecomposition, comprising the steps of: providing a high surface areaporous support having a surface area of at least about 50 m²/g; applyingat least one preselected hydrogen storage compound to said high surfacearea porous support, said at least one preselected compound configuredto alternatively store or release bulk quantities of hydrogen; anddrying said high surface area porous support; whereby said at least onepreselected compound coats said high surface area porous support. 12.The method of claim 11, wherein the step of applying utilizes a methodselected from the group consisting of: depositing, combining, coating,layering, physisorbing, chemisorbing, chemically binding, wetting,polymerizing, and combinations thereof.
 13. A method for storinghydrogen, characterized by the step of: providing a compositioncomprising a high surface area porous support having a surface area ofgreater than or equal to 50 m²/g; and at least one preselected hydrogenstorage compound applied to said high surface area porous support, saidat least one preselected compound configured to alternatively store orrelease bulk quantities of hydrogen at a greater rate and a lowertemperature than said at least one preselected compound not applied tosaid support.
 14. A device, comprising: a composition having a highsurface area porous support having a surface area of greater than orequal to 50 m²/g; and at least one preselected hydrogen storage compoundapplied to said high surface area porous support, said at least onepreselected compound configured to alternatively store or release bulkquantities of hydrogen at a greater rate and a lower temperature thansaid at least one preselected compound not applied to said support.